Water-soluble regenerated fiber production from calluna vulgaris plant species

ABSTRACT

The method disclosed relates to production of regenerated fiber from cellulose-containing plant species, in the textile sector. In particular, the method relates to obtaining water-soluble regenerated cellulose fiber using high or low purity cellulose raw material isolated from the wild plant species of  Calluna Vulgaris.

THE RELATED ART

The invention relates to production of regenerated fiber fromcellulose-containing plant species, in textile sector. The inventionparticularly relates to obtaining water-soluble regenerated cellulosefiber using high or low purity cellulose raw material isolated from thewild plant species of Calluna Vulgaris.

THE PRIOR ART

Throughout history, people have committed themselves to do studies thatfacilitate their lives more and bring innovations all the time.Petrochemistry products that are found almost every part of human lifesince industrial revolution until today compelled people to look foralternative sources due to environmental problems they cause due toremaining in nature for many years without decomposition as well as anumber of health problems. Today, it has become necessary to increaseraw material resources of regenerated fibers that are derived fromcellulose that is the most convenient material for use in nature and tooffer diversity in man-made fiber production.

Regenerated fibers that are a type of chemical fibers are derivedchemically from natural raw materials. Natural raw materials can be usedin textiles by reshaping through chemical processes or turned intofilament or staple fiber.

If cellulose is used as natural polymer that constitutes regeneratedfiber, it is called regenerated cellulosic fiber. Rayon and floss arethe names attributed to regenerated cellulosic fiber in filament form.They are the most important representatives of natural origin man-madefiber production.

While production of (dissoluble) chemical pulp that is rich inalpha-cellulose varied between 4.6 and 5.0 million tons until 1980's,around 1.4 million tons were produced in North America. Since then,production amount decreased to 2.7 million tons due to either productionof alternative products at lower cost for the present or outdatedtechnology of current established systems.

In the prior art, water-insoluble yarn is derived through conventionalregenerated cellulose fiber production methods. Hence, there is a needfor obtaining water-soluble yarn by using natural raw material sourceand renewable cellulose source.

Nowadays, water-soluble filament yarns are derived from polyvinylalcohol polymers. Polyvinylacetate that is derived by means ofpolymerization reaction of vinylacetate is processed with caustic andcomposes polyvinylalcohol polymer. Filament yarn is derived frompolyvinylalcohol (PVA) polymers that are obtained in this way by meansof wet or dry fiber spinning methods.

Recyclability is a required specification for products today.Water-soluble Polyvinylalcohol (PVA) yarn is removed by treating it withformic acid, acetic acid, or citric acid at 100 degrees in dyeing plant.Dissolved PVA polymer cannot be recycled as it is split intoformaldehyde and acetaldehyde groups.

Bath temperature needs to be raised to 100° C. in order to dissolve PVAduring dyeing-finishing processes of raw fabric that is derived from PVAyarns and pliable cotton yarns. In the meantime, PVA polymer formssediments by sticking to the product at rapidly increasing bathtemperatures and direct steam contacts. On the other hand, vinyl acetatethat is raw material of water-soluble conventional PVA yarn is one ofthe xenobiotic organic compounds that are widely used in chemicalindustries. Therefore, this compound is required to be removedefficiently and economically from waste water and waste gases inchemical industries.

Xenobiotic compounds are industrial synthetic compounds released toenvironment at high concentrations. The term “xenobiotic” is describedas substrate or biochemical that is foreign to biologic system ororganism. Lexical meaning of xeno is foreign. Xenobiotic chemicals areproduced in a large number of chemical industries. In recent years,substantial amount of such chemicals are released to environment freely.Benzene, toluene, styrene, xylene, and ethyl benzene are among the mostcommon industrial aromatic products millions of tons of which areproduced a year. Xenobiotics are gradually increasing in urban watersupply systems due to increase in chemical pollution, pesticideapplications, industrial production, use of domestic chemicals, trafficemulsions, and pharmaceutical applications. Xenobiotics also compriseinorganic elements such as heavy metals, metalloids, surfactants, andpreservative substances. While modern chemical industry provides societywith significant benefits, it also causes negative impacts due torelease of xenobiotics to environment. Vinyl acetate falls into thegroup of volatile organic compounds and is included in the list oforganic hazardous air pollutants.

The first patent related to polyvinylalcohol production was taken out byW. O. Herman and W. Haehnel in 1931. However, polyvinylalcohol fiberscame to draw interest in Japan and currently it is mostly produced inJapan. Below is a reaction related to obtaining polyvinylalcohol.

There are two ways of fiber spinning through polyvinylalcohol (PVA)polymers obtained by the abovementioned reaction.

Wet Fiber Spinning Method:

14-16% hot aqueous solution of polyvinylalcohol polymers is prepared.This solution is enabled to solidify by being sprayed from a nozzle andpassing through the precipitation bath comprising Na₂SO₄ and (NH₄)₂ SO₄.

Dry Fiber Spinning Method:

Concentrated aqueous solution of polyvinylalcohol polymers is prepared.The water in the solution that is sprayed from the nozzles is enabled toevaporate (130° C.) and the fibers are solidified. Hot dry air isutilized to vaporize water.

Polyvinylalcohol fibers that are obtained according to both methods areeasily water-soluble. Although this property enables the fibers to beused as catgut in medicine, they must be made water-insoluble for use intextile. For this, the fiber is first subjected to hot processing at210-230° C. for about 20 seconds and bridge connections are establishedbetween macromolecules. Then it is passed through hardening bathscomprising formaldehyde and enables 40% of hydroxyl groups to get intoacetate or ketolisation reactions. Thus, while hydroxyl groups thatenable dissolving in water are eliminated, bridge connections are alsoestablished.

The reactions that occur during hot processing and hardening are asfollows.

Physical Properties:

They are white and shiny. Wet breaking strength of high breakingstrength filaments are 5-7.6 g/denier, and their dry breaking strengthare 6-8.5 g/denier, and their elongation rate is between 10-26% whenwet, and 9-22% when dry.

Wet breaking strengths of staple fibers are 3-2.5 g/denier, and 3.8-6.2g/denier when dry, and their elongation rate is 16-27% when wet, and13-26% when dry. Specific weight of polyvinylalcohol fibers is around1.26-1.30 g/cm³.

In the prior art, there are three types of chemical fiber spinningmethods as

-   -   Wet spinning    -   Dry spinning    -   Soft spinning.

In dry spinning method, the solvents to be used to prepare polymersolution must be volatile, in other words, they must be a substance thathave low boiling point. When such a solution is sprayed from nozzlesunder constant pressure to the chambers through which warm air currentpasses, the solvent is easily evaporated and the polymer substance thatis filament-formed remains. Acetate, triacetate and acrylic fibers areobtained by dry spinning method.

In soft spinning method, the polymers that are not dissolved in anysolvent and have thermoplastic (thermoform) property are turned intofilaments. In this method, the polymer substances in chips form areliquefied (molten) at a temperature above melting point. Molten polymeris sprayed by means of a pump from nozzle heads to the chambers throughwhich cold air current passes under constant pressure. Molten polymer issolidified in filament form in cold chambers. Polyamide, polyester, andpolyurethane fibers are obtained by soft spinning method.

Viscose fiber is typically obtained in two ways.

-   -   Viscose rayon (in filament form)    -   Viscose (in staple form)

To produce viscose, the cellulose raw material obtained from wood andlinter is cleared of foreign substances by processing it with causticsoda and sodium bisulphite. Cellulose pulp is turned into alkalicellulose by processing it with caustic soda solution (NaOH). Cellulosexanthate is obtained by adding carbon sulphur (CS₂) to alkali cellulosefollowing pre-ripening process. It is turned into raw viscose solutionwith the addition of diluted sodium hydroxide. Viscose solution issprayed from the nozzles to an acid bath following filtering andpost-ripening process, and then solidified viscose filaments areobtained by wet spinning method. The filament obtained from single-holenozzle head is called “monofilament”, the one obtained from multi-holenozzle head is called “multifilament”. Viscose rayon yarn is obtained bywrapping solidified filaments on the coil following stretching, washing,and drying processes.

Another method is Lyocell method. In Lyocell method, hot solventdissolves lignin under simultaneous water vapour and intense cutting.This type of production is highly clean and viscose solution can beextruded in diluted solution. This solvent is recovered by dissolvingwithout spinning and washing. Effective solvent recovery is a keycriteria to reduce the cost and for a successful process, and fibers canbe produced in filament and staple form that has circular section.Companies such as Lenzig Couraulds use NMMO as solvent.

Three possible forms of N-methyl morpholine-N-oxide (NMMO) are asfollows.

It is followed a shorter route compared to conventional viscose rayonsystem from the extract to the fiber, and the main difference therein isobserved in regeneration.

Below is the reaction of hydrogen bonds between macromolecules ofcellulose with NMMO organic solvent.

Plant cell and wall is composed of three main components. They arelignin, cellulose, and hemicelluloses. The structure that forms plantstem is the structure sequenced in matrix form. Tree trunks are composedof lignin, cellulose, and hemicelluloses. Cellulose is composed ofglucose units sequenced in chain form. They are first sequenced side byside in chain bundles. Then, they compose cell layers. Hemicelluloses,together with cellulose, are sequenced amorphously beside it. Whilelignin is formless, it covers both celluloses and hemicelluloses.

Wood cells are interconnected with lignin at the middle layer area thatis rich in lignin. The amount of lignin therein is around 25-30% oftotal lignin. Primary cell wall is composed of randomly sequencedcellulose-based microfilaments. Both lignin and cellulose are togethernamed as middle layer.

Secondary cell wall is composed of 3 layers. The main layer is foundbetween the two thin layers. Their thickness varies by cell type andseason. There is one more innermost rough layer in some cells. As themain layer is thick, sequence of its microfilaments is of importance forcellulose. This alignment in cross direction is important in terms ofmechanical and physical strength of fiber. This direction in celluloseis called microfilament angle.

While cellulose chain rings compose the chain by side-by-side sequenceon secondary section of the cell wall, the chains are also sequenced inlayers through side-by-side interconnection. Then, layers are sequencedin overlapping layers. Two different structures are seen in layersequence due to glucose it comprises. These structures are called alphacellulose and beta cellulose. While axes of the crystals on the layersof alpha cellulose are sequenced on the same line, they are sequenced inan obfuscatory manner in beta cellulose.

It is possible to see both sequences in cellulose. This is also calledsequence of cellulose crystals. While alpha sequence is a form ofmetastable sequence, beta sequence has more stable structure. All alphasequences may turn into beta sequence under high pressure and at hightemperature, or in acidic or alkali environment.

95% of the lignin is removed from the wood in which found lignin,cellulose, hemicellulose polymers during extraction processes. Albedo ofwood pulp increases depending on removal of other coloured pigments andlignin amount from it while bleaching. Subjecting the pulp to a seriesof bleaching processes with chemical substances such as chlorine,alkali, hypochlorite, and chlorine dioxide was followed bydisintegrating lignin with oxygen and adding it to the process afterkiering it with chemical substances and before bleaching in 1970's. Inbleaching processes, main objective is to develop processes that reducebleaching costs and minimize environmental effects.

Major bond structures in lignin are given below.

Lignin Disintegration Reactions:

Chips are kier boiled in 20-30 meter high grinding containers at 170° C.for 30 minutes. They are fixed to 140-180° C. under 10 atm pressure.Lower temperature of grinding container is fixed to 65° C.

Lignin is disintegrated following kier boiling process. Lignindisintegration reactions are given below. Lignin is also shown as theabbreviation R—R′ owing to the fact that there are a wide variety ofphenol compounds with large amount of carbon and hydrogen and alsophenol and benzene derivatives in its structure.

R—R′+NaOH→R″COONa+ROH (Reaction of caustic with lignin compounds)

(Lignin: R—R′)

R—R′+Na₂S→Mercaptans: H₂S; NaSH, Na₂S (disintegration reaction withlignin and sodium sulphite)

(a) Chemical recovery (Sodium carbonate is derived from the reaction ofsodium phenols that are formed as a result of the disintegration withoxygen, and caustic is derived from this compound and used indisintegration of lignin in 1^(st) reaction again.)

2NaR+O₂→Na₂CO₃+CO₂

(NaR: Lignin)

(b) Causticization

Na₂CO₃(aq)+Ca(OH)₂(s)→2NaOH(aq)+CaCO₃(s)

CaCO₃→CaO+CO₂

CaO+H₂O→Ca(OH)₂

Kappa Number:

It is the rate of lignin that remains in craft cellulose pulp afterchemical processes. TAPPI-T236 om-99 method employed to determine kappanumber is a method for quantifying the amount of lignin. This method isemployed to determine the degree of relative hardness or bleaching ordelignification degree of the pulp. Kappa number is calculated byconsumption of the solution by volumetric titration method using 0.1 Npotassium permanganate solution at moisture-free pulp under theconditions specified in the method. Low kappa number indicates thatthere is small amount of lignin in the cellulose. Large number indicatesthat there is large number of lignin.

Kappa number is analyzed upon disintegration of lignin and bleachingprocess. Kappa number relates to quality. It is important that kappanumber is low for suitable viscosity in fiber spinning.

In the second half of 1980's and the first half of 1990's, bleachingprocess shifted towards application of chlorine gas and hypochlorite.Elemental free chlorine is single-chlorine based and is abbreviated asECF. In 1990's it was introduced as TCF or Total Free Chlorine. Thisordering, hydrogen peroxide, and ozone processes are added to increaseeffectiveness in bleaching process. Later on, oxygen delignification(lignin degradation) and ozone bleaching processes are added as newprocesses to minimize the effects of environmental wastes, thuspollution is minimized. Lignin disintegration process using oxygencomprises the use of oxygen and alkali to remove a substantial part oflignin after the kiering process. Low kappa number is reached by usingoxygen. Consequently, waste water load of the plant is reduced.

Lignin disintegration process using oxygen occurs at two stages asspecified in Table 1 below. Lignin is disintegrated through oxidizationwith oxidation process following alkali (that is caustic) process.

TABLE 1 Lignin disintegration proces using oxygen O2: Stage 1 Stage 2Application 30 min. 60 min. time Temperature 80-85° C. 90-95° C. Density≥11% ≥11% Pressure 8-10 bar 3-5 bar Final pH 10.5-11

Bleaching processes are covered by TCF and mitigated ECF processes at80-100° C. in a pressurized reactor using peroxide. TCF is theabbreviation of the bleaching process applied without using chlorinedioxide (ClO₂) compound, ECF (elemental chlorine free) is theabbreviation of the bleaching process applied without using chloride(Cl₂) gas. Cl₂ (chloride) or ClO₂ (chlorine dioxide) compounds arehighly reactive chemicals that are used in bleaching processes, andtheir use causes toxic and contaminant wastes. Chlorine or chlorinedioxide compounds react to lignin, form chlorinated organic compoundsand mix in waste water. Use of peroxide, oxygen and ozone chemicals aswell as enzymatic reactions gained importance in bleaching process forenvironmental reasons.

When the reactions that lead to bleaching in peroxide bleaching areanalysed, it is found that the ions having the main bleaching effect areHO₂ and some O₂:

H₂O₂+OH⁻→H₂O+HO₂ ⁻

H₂O₂+2OH⁻→2H₂O+O₂

A part of hydrogen peroxide is disintegrated itself apart from bleachingreactions. This increases the consumption of hydrogen peroxide.Therefore, such reactions need to be prevented.

Prevention of disintegration depends on;

-   -   pH    -   Temperature    -   Time and    -   Stabilizer effect.

The purpose of using stabilizer is to prevent such undesirablereactions.

Hydrogen peroxide stabilizers are known as Sodiumtripolyphosphate(STPP), Sodium hexametaphosphate (SHMP), Ethylenediaminetetraaceticacide(EDTA), Sodiumsilicate (Na₂O.SiO₂), Magnesiumsilicate (MgO.SiO₂). H₂O₂process conditions are given in Table 2 below.

TABLE 2 H₂O₂ Process pH value 9.5-11 Temperature 80-100° C. Pulp density≥11% Time 60-120 min. Pressure 3-5 bar

In order for the reaction in H₂O₂ processes to occur at optimal andefficient level, the reaction environment specified in Table 2 abovemust be ensured. The pulp solution with concentration above 11% istreated with EDTA or the abovementioned stabilizers for 60 to 120minutes. For this reaction environment, pH value must be 9.5-11, thetemperature must be 80-100° C., and the pressure must be 3-5 bar.

Applying the Hemicellulose Enzyme Xylanase:

Xylanase enzymes are used in reservoir towers to reduce consumption ofbleaching agents. Application areas and working conditions of enzymesdepend on certain conditions. For Xylanase enzyme, pH 5-9 andtemperature between 60° C.-90° C. is considered as an application area.Disintegration of hemicellulose is ensured by applying Xylanase enzymeto the pulp at the specified pH and temperature.

Hemicellulose structures are derivatives of heteropolysaccharidescomprised of β-(1-4)-D-xylopyranosyl units between lignin and cellulose.Common name of polymer structures such as xylane, glucuronoxylane,arabinoxylane, glucomannan, and xyloglucane is hemicellulose. They forma chain by being bonded with covalent bond at C2-C3 position.Hemicellulose polymers (DP Polymerization degree: 150-250) have highlyamorphous and irregular branching; they are more sensitive to reactionscompared to cellulose sequenced in straight chains. Xylanhemicellulose,polymer β-(1-4)-D-xylopyranosyl units are given below.

Xylanase enzyme attacks 2^(nd) and 3^(rd) carbons at β-1-4 position inhemicellulose chain and dissolves it into 5-carbon or 6-carbonmonosaccharides. 5-carbon carbohydrates arise from hemicelluloseXylanase enzyme reaction as shown below.

Enzyme activity refers to activity of the enzyme that changes 1 μmolsubstrate in 1 minute and is considered as a unit.

Another method employed to determine bleaching degree of the pulp thatis treated after the reactions is ISO 2470:1999 method. In this method,R rate known as the distribution function measured with reflectometrythat is effective at 44 nm-457 nm wavelength and has internal reflectionindicates the percentage of the reflected radiation. A paper or platehas light absorption (k) and distribution (s) coefficients. Albedo is afunction of k/s. In bleaching process, k remains constant as s decreasesand bleaching degree increases.

In the prior art, the first step of regenerated fiber obtaining methodcomprises removing lignin compounds from the wood structure. In thisstep, while a series of processes mentioned above can be appliedseparately to remove lignin compounds, they can also be used incombination to achieve the desired bleaching and reduce environmentalwaste effects. In wood pulp obtaining processes, Enzymatic (Xylanase)processes are applied in Caustic, ECF (Disintegration of lignin withozone and oxygen), TCF (Disintegration of lignin with ozone and oxygen),and hemicellulose disintegration processes that do not contain chlorineelement or chlorine dioxide compounds mentioned above in order to reduceenvironmental waste effects, and then bleaching degree is adjusted bymeans H₂O₂ process. In the second step, regenerated fiber is obtained byclearing the wood pulp solution of lignin compounds and treating it withN-methyl morpholine-N-oxide solvent.

BRIEF DESCRIPTION OF THE INVENTION

The invention relates to obtaining water-soluble regenerated fiber fromthe plant species of Calluna Vulgaris, which meets the above saidrequirements, eliminates all of the drawbacks, and brings someadditional advantages.

The primary purpose of the invention is to obtain water-soluble polymerfibers with the method of obtaining regenerated cellulose fiber using arenewable cellulose source.

A purpose of the invention is to obtain yarns from Calluna Vulgaris (L.)Hull and Ericaceae plant species, which originates from the same familywith Calluna Vulgaris (L.) Hull.

A purpose of the invention is to obtain water-soluble regenerated fiberfrom Calluna Vulgaris plant species.

The invention also aims to improve the hydrophilicity and softness ofthe final product via environment-friendly water-soluble yarns.

In order to achieve the above said purposes, the invention is formed ofregenerated fibers obtained from Calluna Vulgaris plant.

In order to achieve the above said purposes, the invention is a methodof obtaining regenerated fiber from Calluna Vulgaris plant, and itcomprises the operation steps of:

-   -   Obtaining cellulose pulp from Calluna Vulgaris plant and        performing lignin disintegration,    -   Performing hemicellulose disintegration in the cellulose pulp,    -   Performing bleaching,    -   Adding N-methyl morpholine-N-oxide, water, and        polyethyleneglycol, respectively, and    -   Passing the obtained solution through spinning nozzles.

In order to achieve the purposes of the invention, the operations ofobtaining cellulose pulp and lignin disintegration comprise theoperation steps of:

-   -   Turning Calluna Vulgaris plant into chips,    -   Keeping at ambient temperature for 8 hours via NaOH,    -   baking,    -   grinding,    -   chemical impregnation via Na₂SO₃ and NaOH.

In order to achieve the purposes of the invention, the operation ofhemicellulose disintegration in the cellulose pulp comprises theoperation steps of:

-   -   Adding xylanase enzyme into cellulose pulp,    -   Treating cellulose pulp with xylanase enzyme at 65° C. for 150        minutes, and    -   Washing cellulose pulp.

In order to achieve the purposes of the invention, during the operationof adding N-methyl morpholine-N-oxide, water, and polyethyleneglycol;10-15% by weight cellulose pulp is mixed with 50-65% by weight N-methylmorpholine-N-oxide, 10-20% by weight polyethyleneglycol, and 10-20% byweight water.

In order to achieve the purposes of the invention, the solution obtainedfollowing addition of N-methyl morpholine-N-oxide, water, andpolyethyleneglycol, respectively, to cellulose pulp is subjected tofiber spinning by passing through spinning nozzles. Before fiberspinning operation, said solution is mixed for 20-60 minutes at 30-80°C.

The structural and characteristic features of the invention and all ofits advantages shall be understood better with the below given detaileddescription. Therefore, the assessment should be made by taking intoaccount the detailed descriptions.

DETAILED DESCRIPTION OF THE INVENTION

In this detailed description, the preferred embodiments of thewater-soluble regenerated fiber production from Calluna Vulgaris plantaccording to the invention are only disclosed for better understandingof the subject without forming any limiting effect.

The invention relates to production of water-soluble regenerated fibersfrom Calluna Vulgaris (L.) Hull and Ericaceae plant species thatoriginate from the same family.

Below, the characteristics of Calluna Vulgaris plant are given.

Biological class: Plant

Branches on the family tree: Angiosperms, Eudicots, Asterids

Regnum: Ericales

Family: Ericaceae

Genus: Calluna Salisb

Species: Calluna Vulgaris

Latin name: Calluna Vulgaris (L.) Hull

Calluna Vulgaris is a wild dwarf plant growing in acidic soil in pastureareas in cold winter months. It is a plant species that may threatenbiological diversity in plateaus. It is typically a 0.5-1.25 meter high,evergreen, woody, and scrubby plant. It is pretty wooly in the beginningof growth. Then it becomes bare. It has stalkless leaves that extendthrough the branches; grow in four vertical lines; are green in thebeginning and then become brown; and have wools up to 3.5 mm long. Whileits bell-shaped flowers are pale blue, they may also be pink and white.The flowers grow on the narrow leaves. Its tiny seeds are 0.5 mm longand 0.7 mm wide and in the shape of four-cell round capsules. CallunaVulgaris spreads easily and it may occupy new areas rapidly.

Calluna Vulgaris grows new leaves and shoots beginning from spring toautumn. Its flowers are necklace-shaped and stand suspended downwards,and come into blossom towards the end of autumn. It buds out towards theend of winter. Its seeds germinate all year round. But the bestgermination occurs during spring and autumn. After a forest fire, itbecomes capable of producing seeds in 3 years in that region. Densegreen offshoots of Calluna Vulgaris plant become woody and may liveabout 30 years. Each plant is capable of giving one million seeds persquare meter by producing 3000-4000 flowers and thousands of seeds. Itsweak and tiny looking seeds survive for about 100 years. They are spreadby wind or contact with animals.

The seeds can even germinate only through thermal treatment withoutgetting any light. It can also make vegetative reproduction. CallunaVulgaris comes out in steppes, inside forest lands, and throughout treelines. They are colonized up to 1500 meters height. They are capable ofgrowing in wet and marsh areas; it is extremely resistant to icing.

In the below given Table 3, the development calendar of Calluna Vulgarisis given.

TABLE 3 Development Calendar of Calluna Vulgaris January February MarchApril May June July August September October November DecemberBlooming + + + + Vegetative + + + + + + + + growthReproduction + + + + + form Seeding + + + + +Germination + + + + + + + + +

Other species covered are named in Latin as Erica Cinera, EricaLusitanica, and Erica Manipuliflora Salisb. They are found in Giresun,Trabzon, Rize, Artvin, and Istanbul in Turkey.

The fact that this plant is capable of growing in acidic soils andwinter months; each plant is capable of giving one million seeds persquare meter by producing 3000-4000 flowers and thousands of seeds; andit can grow in marsh areas are the most significant characteristics ofthe wild plant, Calluna Vulgaris. It spreads easily and invades newareas quickly.

Cellulosic Substance Analysis in Calluna Vulgaris Plant Structure ViaChemical Methods

Lignin and Cellulose Separation Methods Via Acid-Detergent Method

Evaluation is made for grass, hay, bush, and tree via ligninacid-detergent separation method. Cellulose is hydrolyzed in isolationwith 72% sulphuric acid (H₂SO₄). The reaction of the chemical substancesused in the acid-detergent method leads to substantial dissolution ofhemi-cellulose and allows calculating the amount of the remainingalpha-cellulose.

-   -   CTAB (Cetyltrimethyl-ammonium bromide); 50 g of Cetyl trimethyl        ammonium bromide is found in 5 litres of 0.5 Molar H₂SO₄.

Procedure: 100 ml of CTAB solution is added into a 250 ml beakercontaining 0.500-1.000 g of dry material, and a few drops of octan-2-olis dropped as an anti-foaming agent. The beaker is stirred for 1 hour.The obtained solution is passed through the previously weighed No. 2sinter (W2) filter under pressure vacuum. The remaining precipitate iswashed three times with boiling deionised water/acetone until it becomescolourless. The precipitate is dried at 105° C. for 2 hours, cooled in adessicator, and weighed (W3). With this analysis method, the amount ofcellulose found in C. Vulgaris plant can be determined.

% ADF=(W3−W2)*100/WI

-   -   Reaction chemicals: Sulphuric acid (72% W/V) 720 ml H₂SO₄ is        added into 540 ml deionised water.

Procedure: a sample smoothly ground with 72% H₂SO₄ (15° C.) is mixeduntil it turns into a cake and placed in a suitable container. 3 hourslater, it is washed with non-acidic water, vacuumed, dried for 2 hoursat 105° C., cooled in a dessicator, and weighed (W4). The solid portionis combusted for 2 hours in a furnace at 550° C., cooled in adessicator, and weighed (W5).

% LIGNIN=(W4−W5)*100/WI

% CELLULOSE=(W3−W4)*100/WI

With this application, % LIGNIN and % CELLULOSE amounts are determined.

In the below given Table 4, dry weight % of the cellulose found in allof the Calluna Vulgaris plant via ADF extraction is given.

Below given results are obtained with the above given two applications.

TABLE 4 dry weight % of the cellulose found in all of the CallunaVulgaris plant obtained by ADF extraction Holocellulose Hemi-celluloseAlpha cellulose Genus of Plant (% Dry weight) (% Dry weight) (% Dryweight) Calluna Vulgaris 36.6 15.2 21.4

In the below given Table 5, among the chemical compounds found in thestructure of Calluna Vulgaris plant, dry weights of proteins (PRO);lipid (LIP); phenol (PHE); undefined carbohydrates (TNC); and minerals(ASH) are given in mg/g.

TABLE 5 Chemical analysis results of Calluna Vulgaris plant PRO LIP PHECEL LIG VAKS TNC ASH mg/g mg/g mg/g mg/g mg/g mg/g mg/g mg/g TOTAL 27 1432 450 151 10 45 68 854

Table 5 provides the chemical analysis results of Calluna Vulgaris plantThe cellulose, lignin, and fat samples forming the cellular walls areextracted in order to determine their amounts. The samples are purifiedby being treated in turn with the natural detergent solution formed ofdisodium ethylene-diaminetetra acetate dihydrate, sodium boratedecahydrate, disodium hydrogen phosphate chemicals anddecahydronaphthaline, acetone, and sodium sulphide.

Samples in equal amounts are treated with acid detergent solution(sulphuric acid 1 N and cetyltrimethyl ammonium bromide) so as to removehemi cellulose. Afterwards, they are treated with potassium permanganateto remove lignin. And then, cellulose is removed by sulphuric acid (72%W/W). Remaining oils and minerals are removed by combustion in acrematorium for 3 hours at 500-550° C. The minerals are determined afterkeeping the material in crematorium for 5 hours at 550° C.

Protein amount (PRO): Total nitrogen amount is determined by usingKjeldahl method.

Lipid (LIP): Determined by diethyl ether extraction for 8 hours in aSoxhlet extractor. Phenols having different molecular weights aretreated at 70° C. with pure methanol and 50% aqueous methanol solution,respectively. It is colorimetrically determined by using Folin-ciocalteuchemical substance.

For total anonymous amylase activation structures; the endo andexonuclease α- and β amylase activation is determined by usingHajedorn-jensen volumetric method following 48 hours of incubation at37° C.

The above-mentioned methods are general analysis methods applied onCalluna Vulgaris plant and as well as used in determination of protein,oil cellulose, lignin amounts in all plants.

In Calluna Vulgaris plant, α-amyrin, β-amyrin, oleanolic acid,taraxerol, and ursolic acid etc. compounds determined by using supercritical carbondioxide extraction method are known as triterpenoids.Below, enumerated carbon frameworks of triterpenoids are given.

Moreover, below, triterpenoids found at the leaves, roots, and stems ofCalluna Vulgaris plant are given in μg/g dry weight.

TABLE 6 triterpenoids found at the leaves, roots, and stems of CallunaVulgaris plant (μg/g dry weight) Leaves Roots Stems α-amyrin 35,000 3703,900 β-amyrin 13,000 550 5,700 Leupeol 19,000 0 0 Oleanolic acid 11,00055 14,000 Taraxerol 0 610 0 Taraxer-4-1 0 490 0 Ursolic acid 52,000 13034,000 Unnamed ursolic 26,000 20 7,500 acid

Biological activity of Calluna Vulgaris plant: Ursolic acid andoleanolic acid compounds show anti-cancer characteristics againstleukaemia cells, gastritic tumors and lung tumors. Since it hastriterpenoid compounds, it has antiulcerous and antimicrobial biologicalactivity.

Below, the production method of water-soluble regenerated fibers fromCalluna Vulgaris (L.) Hull according to the invention and Ericaceaeplant species that originate from the same family.

The method of obtaining regenerated fiber from Calluna Vulgaris plantbasically comprises the operation steps of:

-   -   Obtaining cellulose pulp from Calluna Vulgaris plant and        performing lignin disintegration,    -   Performing hemicellulose disintegration in the cellulose pulp,    -   Performing bleaching,    -   Adding N-methyl morpholine-N-oxide, water, and        polyethyleneglycol, respectively, and    -   Passing the obtained solution through spinning nozzles.

First of all, kraft cellulose pulp is obtained from Calluna Vulgarisplant and lignin disintegration operation is performed. For obtainingthis pulp, Calluna Vulgaris plant is mechanically turned into chipsform. Penetration is ensured by keeping the material at ambienttemperature for 8 hours with 3.0% NaOH, and then it is baked in apressurised container for 1 hour at 125° C. Following baking operation,it is ground for 10 minutes in pressureless vapour. Chemicalimpregnation is made with 2-3% Na₂SO₃ and 1-7% NaOH, and treated for 5minutes at 60-120° C. At the stage of obtaining kraft cellulose pulp,lignin disintegration is also performed in the same process.

Xylanase enzyme is applied on kraft cellulose pulp for disintegratinghemicellulose polymer structures. Enzyme dosage, 0.5 kg/ton; applicationtime, 150 minutes; temperature, 65° C.; density, 10%; pH 8.5-8.7; andxylanase enzyme activity is 5000 IU/ml. The pulp treated with enzyme isthen washed with distilled water.

Kraft cellulose pulp treated with xylanase enzyme is then beached withhydrogen peroxide (H₂O₂). Bleaching is applied on kraft cellulose pulpwith 1.5% NaOH, 0.5% sodium silicate, 0.1% MgSO4, 4% H₂O₂, and at 90° C.and 3-5 atm pressure, for 180 minutes. The pH value and viscosity of thekraft cellulose solution (pulp) are 11 and 14.7 mPas, respectively.

The lignin amount in the pulp is found using ISO 2470 method(luminosity=51%) and TAPPI-T236 om-99 method (Kappa No.=9.72).

As the lignin amount found in wood pulp solution increases, the kappaNo. rises and the luminosity is reduced. More yellowish or brownishsolution pulp is obtained. It is not possible to pass such a solutionthrough spinning nozzles under pressure and obtain fibers. Since thissolution will have resistance against fluidity, high pressure isrequired for obtaining fiber by passing the solution through spinningnozzles; but such high pressures are not possible due to the mechanicalstructures of the spinning nozzles. However, a pulp solution having thebelow given viscosity, kappa value, and luminosity characteristics wouldoptimally allow performing fiber spinning.

1. Viscosity: 14.7 mPas

2. Kappa No.=9.72

3. Luminosity=51%

55% amine oxide NMMO, 20% PEG, 10% water, 15% cellulose pulp mixture areprepared in a container and mixed at 30-70° C. at 40 RPM for 60 minutes.The preferred rates in said mixture are given below in table form.

TABLE 7 PEG/NMMO/Water/Cellulose mixing rates Preferred Usable amount byamount by Ingredient weight (%) weight (%) Cellulose pulp obtained from15 10-15 Calluna Vulgaris plant N-methylmorpholine- 55 50-65 N-oxide(NMMO) Water 10 20-10 Polyethyleneglycol (PEG) 20 20-10

Cellulose-Amine Oxide (NMMO)-Polyethyleneglycol (PEG) solution: 10-15%cellulose, 50-65% amine oxide (NMMO), 10-20% PEG, and 10-20% water.Through the spinning nozzles; cellulose solution completes molecularorientation via wet spinning method.

With wet fiber spinning method; a solution consisting of polyethyleneglycol, NMMO, cellulose pulp, and water is mixed for 20-60 minutes at30-80° C., and then fiber spinning is performed by using spinningnozzles made of stainless steel, nickel, or platinum alloys with nozzlechannel diameters ranging between 0.2-1 mm.

In the cellulose pulp obtained from Calluna Vulgaris plant, the ligninmaterial is required to be removed completely. Viscosity of polyethyleneglycol/water/cellulose/NMMO solution should be fluid such that it wouldnot prevent formation of yarn. The fiber diameter increases as theviscosity increases.

While cellulose is mixed with 10-20% PEG and 50-65% aqueous amine oxide(NMMO) solution, cellulose activation temperature increases up to 60° C.Cellulose swells in polar media such as water. The temperature ofswollen cellulose increases up to 70° C. in amine oxide (NMMO)-watermixture. If this temperature is maintained for about 60 minutes,cellulose activation is completed. In this way, good mixture andhomogeneous cellulose melt are obtained. Before the formed solutionturns into solid chips and granule form, subvention can be made to thespinning part. Homogeneous polymer melt or solution is a key producthaving smooth spinning performance and final product characteristics.

Different from the traditional raw material sources of other regeneratedfibers, within the scope of the invention, regenerated fiber is obtainedby using Calluna Vulgaris (L.) Hull and Ericaceae plant species from thesame family. As the organic solvent, N-methyl morpholine-N-oxide isused. Polyethylene glycol polymer structure that can form amorphousgroups is preferred. Viscosity is reduced by using polyethylene glycolpolymer. Moreover, the hydrogen bridge bonds among the cellulose macromolecules are reduced by using a polyethylene glycol polymer structure.Polyethylene glycol polymer is water dissoluble. The yarn obtained fromregenerated fibers according to the invention can be dissolved in waterby using cellulose enzymes or acidic solutions. Attraction force occursbetween each solution having partial electronegative charge δ− andhydrogen atoms found in cellulose macro molecules and having partialpositive δ+ charge. Bond polarity increases with the partial attractiveforces between the hydrogen groups having partial positive δ+ charge inthe solution polymer also containing the solvent substance and theoxygen or halogen groups in the solvent substance having negativecharge.

Cellulose material found in Calluna Vulgaris plant is utilized ascellulose raw material source and water-soluble polymer yarn can beobtained from this raw material by using regenerated cellulose fiberobtaining methods. Hydrophilicity and softness of the final product areimproved with environment-friendly water-soluble yarns.

Water-soluble fibers cannot be obtained with traditional regeneratedcellulose fiber obtaining methods. Thanks to the invention,water-soluble polymer fiber can be produced via regenerating method byusing renewable cellulose source. Moreover, water-soluble regeneratedcellulose fibers can be re-used as cellulose polymers via recyclingprocess. Conventional PVA polymer known as water-soluble polymer isseparated into acetaldehyde or formaldehyde molecules as a result ofdissolving in acetic acid or formic acid at high temperatures, andcannot be used in recycling processes.

Cellulose pulp obtained after removing lignin, pectin etc. substancesfrom Calluna Vulgaris plant containing 21.4% cellulose is treated withN-methylmorpholine-N-oxide solvent, and thus modified fiber is obtained.Since the degree of polymerization of cellulose polymers forming thesefibers are low, they dissolve in water when they are treated withcellulose enzyme. Therefore, the fibers according to the invention canbe used in place of PVA (polyvinyl alcohol).

Different from natural fibers, cellulose macro molecules formingregenerated cellulose fiber have low average polymerization (OP)degrees. OP degrees of cellulose materials or linters used as rawmaterial in obtaining regenerated cellulose fibers are actually not thatlow. However, as the polymerization degrees of macro molecules increase,the viscosities of their solutions also increase in parallel. Since veryhigh pressure is required for passing high viscosity solutions smoothlythrough small nozzle holes, cellulose macro molecules are partiallydisintegrated while preparing fiber solution. The polymerization degreesof cellulose macro molecules used for obtaining fibers is required to beabove 200.

As a significant result of seeing low average polymerization degrees incellulose macro molecules that form normal regenerated cellulose fibers,these fibers have much lower wet strength compared to dry strength (wetbreaking strength is about 55-65% of dry breaking strength).

Polyethyleneglycol polymer structure is formed of hydrogen bonds betweencellulose macromolecules and N-methyl morpholine within fiber spinningsolution. In this way, since the strength of hydrogen bonds and VanderWaals attraction forces among cellulose macro molecules would bereduced, the wet strength of obtained fibers is lower. Therefore, theyare dissolved easily in water by using cellulose enzymes indye-treatment processes.

Since polyethyleneglycol reduces viscosity, the hydrogen bonds andVander Waals attraction forces are reduced among cellulose macromolecules. As a result, weaker macromolecular cellulose polymer isobtained. Since the amorphous region of said fibers is 30-40% more thantraditional regenerated fibers and they have lower wet strength, theycan easily be dissolved in cellulose enzyme solution at 50° C.-60° C.temperature. Already short cellulose macro molecules of regeneratedcellulose fibers cannot be placed uniformly within the fiber. Therefore,a big portion of these fibers (about 80-85%) is formed of amorphousregions. Non-uniform arrangement of macro molecules reduces theattractive forces among these molecules as well as reducing their wetstrength, and at the same time, causes their water and aqueous flottesto impact on amorphous regions in a simpler and more effective manner.

In spinning bath, polyethyleneglycol, NMMO, and cellulose solution isoriented with wet spinning method in an extruder at 30-80° C.temperature range.

Below, a reaction scheme is given, which shows that polyethyleneglycolmolecule forms hydrogen bonds between NMMO and cellulose macro moleculesand thus prevents formation of hydrogen bridge bonds between the solvent(N-methyl morpholine N-oxide) and cellulose macro molecules, and allowsformation of amorphous structures among cellulose macro molecules.

Amorphous regions are formed among cellulose macro molecules by using10-20% polyethylene glycol polymer. During the dyeing process of thisyarn having lower wet strength, its removal by using cellulose enzyme ismuch easier. In this way, yarns obtained from cellulose raw materialwith this method become water soluble. Polyethylene glycol polymer is aneasily water soluble polymer. It is an organic product compared toobtaining process steps of polyvinyl alcohol yarn. Polyvinyl alcoholyarn commonly used in textile sector is used in specific processes dueto is water soluble characteristics. Yet, hydrocotton products can alsobe referred to as organic production, since regenerated cellulose yarnobtained with polyethylene glycol process is used instead of polyvinylalcohol yarn, the regenerated cellulose yarn is an organic product, andthe process method is suitable.

Polyethylene glycol polymer forms hydrogen bonds between cellulose macromolecules during fiber spinning. By means of these hydrogen bonds, whiletheir dry strength reaches 7-9.5 g/denier levels, their wet breakingstrength is reduced down to 3-5.5 g/denier levels. Their specific weightis around 1.35-1.45 g/cm³.

During application, the yarns obtained with the method according to theinvention are not required to be treated with formic acid or acetic acidat 90-100° C. temperature during additional bath before bleachery anddyeing, as in removal processes of PVA yarns from raw materials.Application of pilling operation found in dyeing process is adequateinstead of this process. In the pilling operation, cellulose enzyme isapplied at 2-3 g/L, pH 5-5.5, and 50-60° C. for 30 minutes.

It is possible to use polyvinylchloride polymer structure instead ofpolyethylene glycol. Hydrogen bridge bonds can be formed betweencellulose macro molecules by forming amorphous groups with this polymer.Moreover, wet or dry spinning processes can be developed by usingpolyvinylchloride/NMMO/water solvents. Accordingly, following obtainingof yarn via fiber spinning from polymers that can form hydrogen bridgebonds with cellulose macro molecules, yarns that can easily be removedin water can be obtained by using enzyme or solvents.

An attraction force occurs between each polymer having partialelectronegative charge δ− and hydrogen atoms found in cellulose macromolecules and having partial positive δ+ charge.

NMMO/H₂O/PEG are used as solvents. Regenerated cellulose fiber isobtained by forming cellulose solution, NMMO determined as amine-oxide,and the yarns obtained from these fibers are made water-soluble usingcellulose enzyme.

1. Regenerated fiber obtained from Calluna Vulgaris plant.
 2. A methodof obtaining regenerated fiber from Calluna Vulgaris plant,characterized in that; it comprises the operation steps of: obtainingcellulose pulp from Calluna Vulgaris plant and performing lignindisintegration; performing hemicellulose disintegration in the cellulosepulp; performing bleaching; adding N-methyl morpholine-N-oxide, water,and polyethyleneglycol, respectively; and passing the obtained solutionthrough spinning nozzles.
 3. The method according to claim 2,characterized in that; the operations of obtaining cellulose pulp andlignin disintegration comprise the operation steps of: turning CallunaVulgaris plant into chips; keeping at ambient temperature for 8 hoursvia NaOH; baking; grinding; and; chemical impregnation via Na₂SO₃ andNaOH.
 4. The method according to claim 2, characterized in that; theoperation of hemicellulose disintegration in the cellulose pulpcomprises the operation steps of: adding xylanase enzyme into cellulosepulp; treating cellulose pulp with xylanase enzyme at 65° C. for 150minutes; and washing cellulose pulp.
 5. The method according to claim 2,characterized in that; during the operation of adding N-methylmorpholine-N-oxide, water, and polyethyleneglycol, it comprises theoperation step of mixing 10-15% by weight cellulose pulp with 50-65% byweight N-methyl morpholine-N-oxide, 10-20% by weight polyethyleneglycol,and 10-20% by weight water.
 6. The method according to claim 2,characterized in that, it comprises the operation step of performingfiber spinning by passing the solution obtained following addition ofN-methyl morpholine-N-oxide, water, and polyethyleneglycol,respectively, to cellulose pulp, through spinning nozzles.
 7. The methodaccording to claim 6, characterized in that, before the fiber spinningoperation, it comprises the operation step of mixing said solution for20-60 minutes at 30-80° C.